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Click chemistry refers to selective reactions developed for grafting of bio(macro)molecules in their biological media. Caged click compounds have been employed to spatiotemporally control click reactions. Here, we survey the uncaging of photo-dibenzocyclooctyne-OH (photoDIBO-OH) to its click-chemistry active form DIBO-OH, with particular attention to its conversion timescale and efficiency. Ultraviolet pump–infrared probe experiments reveal a stepwise decarbonylation: first, carbon monoxide (C≡O) is released within 1.8 ps, and then, it converts, within 10 ps, to DIBO-OH. Completion of uncaging is achieved with an efficiency of ∼50%. A successful demonstration of two-photon uncaging of photoDIBO-OH at long wavelength (700 nm) confers enhanced in vivo compatibility and proceeds on the same timescale. [ABSTRACT FROM AUTHOR]

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO2-based supports through H2 reduction pretreatment. The Pt catalysts supported by defective CeO2-based supports, including CeO2, CeZrOx, and CeO2/Al2O3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (PtC) with the bottom layer of Pt atoms substituting the Ce cations in the CeO2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O2 activation at PtC-CeO2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.

First-ever measurements of particulate matter (PM2.5, PM10, and TSP) along with gaseous pollutants (CO, NO2, and SO2) were performed from June 2019 to April 2020 in Faisalabad, Metropolitan, Pakistan, to assess their seasonal variations; Summer 2019, Autumn 2019, Winter 2019-2020, and Spring 2020. Pollutant measurements were carried out at 30 locations with a 3-km grid distance from the Sitara Chemical Industry in District Faisalabad to Bhianwala, Sargodha Road, Tehsil Lalian, District Chiniot. ArcGIS 10.8 was used to interpolate pollutant concentrations using the inverse distance weightage method. PM2.5, PM10, and TSP concentrations were highest in summer, and lowest in autumn or winter. CO, NO2, and SO2 concentrations were highest in summer or spring and lowest in winter. Seasonal average NO2 and SO2 concentrations exceeded WHO annual air quality guide values. For all 4 seasons, some sites had better air quality than others. Even in these cleaner sites air quality index (AQI) was unhealthy for sensitive groups and the less good sites showed Very critical AQI (> 500). Dust-bound carbon and sulfur contents were higher in spring (64 mg g-1) and summer (1.17 mg g-1) and lower in autumn (55 mg g-1) and winter (1.08 mg g-1). Venous blood analysis of 20 individuals showed cadmium and lead concentrations higher than WHO permissible limits. Those individuals exposed to direct roadside pollution for longer periods because of their occupation tended to show higher Pb and Cd blood concentrations. It is concluded that air quality along the roadside is extremely poor and potentially damaging to the health of exposed workers.

A merged potential energy surface (PES) is introduced for CO + CO collisions by combining a recent full-dimensional ab initio PES [Chen et al. J. Chem. Phys. 153, 054310 (2020)] and analytical long-range multipolar interactions. This merged PES offers a double advantage: it retains the precision of the ab initio PES in describing the van der Waals well and repulsive short range while providing an accurate physical description of long-range interaction; it significantly reduces the computational time required for trajectory integration since the long-range portion of the ab initio PES (involving numerous neural network fitting parameters) is now replaced by the analytical model potential. Based on the present merged PES, mixed Quantum-Classical (MQC) calculations, which capture quantum effects related to vibrational motion, align with a range of experimental data, including transport properties, vibrational energy transfer between CO and its isotoplogues, as well as rate coefficients for V–V and V–T/R processes. Notably, the original ab initio PES yields V–T/R rate coefficients at low temperatures that are significantly higher than the experimental data due to the artificial contribution of its unphysical long-range potential. In addition to conducting extensive MQC calculations to obtain raw data for V–V and V–T/R rate coefficients, we employ Gaussian process regression to predict processes lacking computed MQC data, thereby completing the considered V–V and V–T/R datasets. These extensive rate coefficient datasets, particularly for V–T/R processes, are unprecedented and reveal the significant role played by V–T/R processes at high temperatures, emphasizing the necessity of incorporating both V–V and V–T/R processes in the applications. [ABSTRACT FROM AUTHOR]

We describe Reflection Absorption Infrared Spectroscopy (RAIRS) and first-principles Density Functional Theory (DFT) studies of ammonia adsorption on the Cu{311} surface. Our experimental results indicate an upright chemisorbed species at low coverages, with at least one additional species accompanying this at higher coverages. Our high-coverage RAIRS data cannot be fully explained by DFT models containing only ammonia or its dissociation products, even allowing for molecular tilt and/or the formation of a bilayer. We therefore also consider urea and formamide as possible products of surface reaction with residual carbon monoxide, but these species are again not fully compatible with our observed spectra. The overlayer composition at high coverages remains mysterious. [ABSTRACT FROM AUTHOR]

In this work, we revisit the dynamics of carbon monoxide molecular chemisorption on Cu(110) by using quasi-classical trajectory calculations. The molecule–surface interaction is described through an atomistic neural network approach based on Density Functional Theory calculations using a nonlocal exchange–correlation (XC) functional that includes the effect of long-range dispersion forces: vdW-DF2 [Lee et al. Phys. Rev. B, 82, 081101 (2010)]. With this approach, we significantly improve the agreement with experiments with respect to a similar previous study based on a semi-local XC functional. In particular, we obtain excellent agreement with molecular beam experimental data concerning the dependence of the initial sticking probability on surface temperature and impact energy at normal incidence. For off-normal incidence, our results also reproduce two trends observed experimentally: (i) the preferential sticking for molecules impinging parallel to the [ 1 ̄ 10] direction compared to [001] and (ii) the change from positive to negative scaling as the impact energy increases. Nevertheless, understanding the origin of some remaining quantitative discrepancies with experiments requires further investigations. [ABSTRACT FROM AUTHOR]

Purpose: Total hemoglobin mass (tHbmass) and blood volume (BV) are important determinants of maximal oxygen uptake and endurance capacity. Higher-caliber endurance athletes usually possess higher tHbmass and BV values. This study aimed to compare tHbmass and BV among swimmers of diverse competitive calibers and distances. Methods: Thirty swimmers (16 female and 14 male) participated in the study: 3 were tier 5, world class (869 [59] FINA points); 15 were tier 4, elite/international (853 [38] points); and 12 were tier 3, highly trained/national (808 [35] points). They specialized in competition distances ranging from 200 m to open-water 10 km. Between February 2019 and February 2020, all swimmers had their tHbmass and BV measured by carbon monoxide rebreathing 1 to 6 times and participated in multiple competitions and race events. Results: Relative tHbmass and BV were not different (P >.05) between tiers among women or among men (pooled tHbmass values 14.5 [0.5], 12.5 [1.5], 12.6 [2.3] g/kg for tier 5, tier 4, and tier 3, respectively). No differences were observed in relative tHbmass (P =.215) and BV (P =.458) between pool and open-water swimmers or between 200-, 400-, and 1500-m specialists (P >.05). No significant correlations were found between the highest measured absolute or relative tHbmass and BV and the highest FINA points scored over the follow-up period (R = −.42–.17, P =.256–.833), irrespective of competition distance. Conclusion: tHbmass and BV values did not differ between swimmers of different calibers or among competition distances. Furthermore, these values did not correlate with FINA points, either in males or in females. The present results indicate that hematological characteristics may have a lesser impact on swimming performance than on land-based endurance sports. [ABSTRACT FROM AUTHOR]

The unique physical properties of carbyne, a novel carbon nanostructure, have attracted considerable interest in modern nanotechnology. While carbyne synthesis has been accomplished successfully using diverse techniques, the underlying mechanisms governing the carbon monoxide-dependent catalytic synthesis of endohedral carbyne remain poorly understood. In this simulation-based study, we investigate the synthesis of endohedral carbyne from carbon and carbon monoxide radicals in the presence of a nickel catalyst inside double-walled carbon nanotubes with a (5,5)@(10,10) structure. The outcome of our investigation demonstrates that the incorporation of the carbon atom within the Nin@(5,5)@(10,10) model system initiates the formation of an elongated carbon chain. In contrast, upon the introduction of carbon monoxide radicals, the growth of the carbyne chain is inhibited as a result of the oxidation of endohedral nickel clusters by oxygen atoms after the initial steps of nucleation. Our findings align with prior theoretical, simulation, and experimental investigations, reinforcing their consistency and providing valuable insights into the synthesis of carbyne-based nanodevices that hold promising potential for future advancements in nanotechnology. [ABSTRACT FROM AUTHOR]

Carbon monoxide poisoning is one of the most common forms of poisoning in the world. Although the primary mode of treatment, oxygen therapy, is highly effective in many cases, there are instances in which it is inadequate or inappropriate. Whereas oxygen therapy relies on high levels of a low-affinity ligand (O2) to displace a high-affinity ligand (CO) from metalloproteins, an antidote strategy relies on introducing a molecule with a higher affinity for CO than native proteins (Kantidote,CO > Kprotein,CO). Based on the fundamental chemistry of CO, such an antidote is most likely required to be an inorganic compound featuring an electron-rich transition metal. A review is provided of the protein-, supramolecular complex-, and small molecule-based CO poisoning antidote platforms that are currently under investigation.

We evaluated whether veterans with Gulf War illness (VGWI) report greater ionizing radiation adverse effects (RadAEs) than controls; whether radiation-sensitivity is tied to reported chemical-sensitivity; and whether environmental exposures are apparent risk factors for reported RadAEs (rRadAEs). 81 participants (41 VGWI, 40 controls) rated exposure to, and rRadAEs from, four radiation types. The relations of RadAE-propensity (defined as the ratio of rRadAEs to summed radiation exposures) to Gulf War illness (GWI) presence and severity, and to reported chemical-sensitivity were assessed. Ordinal logistic regression evaluated exposure prediction of RadAE-propensity in the full sample, in VGWI, and stratified by age and chemical-sensitivity. RadAE-propensity was increased in VGWI (vs. controls) and related to GWI severity (p

While polymeric carbon monoxide (pCO) has been experimentally found to remain amorphous and undecomposed at room temperature up to 50 GPa, the question of whether crystalline counterparts of it can be obtained naturally raises. From different computational studies, it can be inferred that either the crystallization of amorphous pCO (a-pCO) or its decomposition into a mixture of CxOy suboxides (x > y) or carbon and CO2 may occur. In this study, we report experimental investigations of the high temperature (700–4000 K) transformation of a-pCO in the 47–120 GPa pressure range, conducted by x-ray diffraction in laser heated diamond anvil cells. Our results show the formation of no crystalline phases other than CO2 phase V, thus indicating the decomposition of the pristine a-pCO into CO2 and, likely, a mixture of amorphous CxOy suboxides and amorphous carbon hardly detectable at extreme conditions. These results support the theoretical picture of the pCO decomposition. We also show that the pressure-temperature kinetic border for this decomposition is very steep, thus indicating a strongly pressure-dependent kinetic barrier. [ABSTRACT FROM AUTHOR]

Intensities of 14 lines in the sixth overtone (7–0) band of carbon monoxide (12C16O) are measured in the visible range between 14 300 and 14 500 cm−1 using a frequency-stabilized cavity ring-down spectrometer. This is the first observation of such a high and weak overtone spectrum of the CO molecule. A theoretical model is constructed and tested based on the use of a high accuracy ab initio dipole moment curve and a semi-empirical potential energy curve. Accurate studies of high overtone transitions provide a challenge to both experiment and theory as the lines are very weak: below 2 × 10−29 cm molecule−1 at 296 K. Agreement between theory and experiment within the experimental uncertainty of a few percent is obtained. However, this agreement is only achieved after issues with the stability of the Davidson correction to the multi-reference configuration interaction calculations are addressed. [ABSTRACT FROM AUTHOR]

Background: Air pollution causes many respiratory disorders, especially in children and the elderly. These disorders include asthma exacerbations, bronchiolitis, and pneumonia. Research on the association between air pollution and respiratory disorders helps to reevaluate environmental policies in developing countries. Methods: This descriptive cross-sectional study was conducted on 932 children with respiratory manifestations admitted from December 2017 to December 2019 at the Emergency Department of Akbar Children's Hospital of Mashhad University of Medical Sciences, Mashhad, Iran. Air pollution indices such as concentration of sulfur dioxide (SO2), nitrogen dioxide (NO2), carbon monoxide (CO), and particulate matter (PM) smaller than 2.5 and 10 μm and other parameters, including the air quality index (AQI), air temperature, and humidity level from 2017 to 2019, were retrieved from Mashhad Environmental Pollution Monitoring Center. Demographic and clinical data of patients were collected from patients' hospital documents. We used descriptive analytical methods such as central tendency, variability, and frequency distribution to report and analyze demographic and clinical data through tables and diagrams. The association between air pollution indices and respiratory manifestations was examined by the Spearman correlation test. The correlation between the AQI and total hospital admissions and asthma-related hospital admissions was also evaluated by the Spearman correlation test. Results: Hospital admissions due to respiratory manifestations were not associated with the AQI of each month (p-value = 0.794). The concentration of SO2 was correlated with respiratory-related hospital admissions (correlation coefficient = 0.487, p-value = 0.016) but not asthma attacks. Conclusion: Generally, our cross-sectional study showed no statistically considerable association between air pollution and hospital admissions due to respiratory manifestations and asthma attacks in children. Of the air pollution indices, only SO2 concentration was associated with respiratory-related hospital admissions but not asthma attacks. [ABSTRACT FROM AUTHOR]

Background: Carbon monoxide (CO), hypothetically linked to prebiotic biosynthesis and possibly the origin of the life, emerges as a substantive growth substrate for numerous microorganisms. In anoxic environments, the coupling of CO oxidation with hydrogen (H2) production is an essential source of electrons, which can subsequently be utilized by hydrogenotrophic bacteria (e.g., organohalide-respring bacteria). While Dehalococcoides strains assume pivotal roles in the natural turnover of halogenated organics and the bioremediation of chlorinated ethenes, relying on external H2 as their electron donor and acetate as their carbon source, the synergistic dynamics within the anaerobic microbiome have received comparatively less scrutiny. This study delves into the intriguing prospect of CO serving as both the exclusive carbon source and electron donor, thereby supporting the reductive dechlorination of trichloroethene (TCE). Results: The metabolic pathway involved anaerobic CO oxidation, specifically the Wood-Ljungdahl pathway, which produced H2 and acetate as primary metabolic products. In an intricate microbial interplay, these H2 and acetate were subsequently utilized by Dehalococcoides, facilitating the dechlorination of TCE. Notably, Acetobacterium emerged as one of the pivotal collaborators for Dehalococcoides, furnishing not only a crucial carbon source essential for its growth and proliferation but also providing a defense against CO inhibition. Conclusions: This research expands our understanding of CO's versatility as a microbial energy and carbon source and unveils the intricate syntrophic dynamics underlying reductive dechlorination. 3ez2V3iuLHAKAp3AxS5o4q Video Abstract [ABSTRACT FROM AUTHOR]

In August 2017, a smoke plume from wildfires in British Columbia and the Northwest Territories recirculated and persisted over northern Canada for over two weeks. We compared a full‐factorial set of NASA Goddard Institute for Space Studies ModelE simulations of the plume to satellite retrievals of aerosol optical depth and carbon monoxide, finding that ModelE performance was dependent on the model configuration, and more so on the choice of injection height approach, aerosol scheme and biomass burning emissions estimates than to the choice of horizontal winds for nudging. In particular, ModelE simulations with free‐tropospheric smoke injection, a mass‐based aerosol scheme and comparatively high fire NOx emissions led to unrealistically high aerosol optical depth. Using paired simulations with and without fire emissions, we estimated that for 16 days over an 850,000 km2 region, the smoke decreased planetary boundary layer heights by between 253 and 547 m, decreased downward shortwave radiation by between 52 and 172 Wm−2, and decreased surface temperature by between 1.5°C and 4.9°C, the latter spanning an independent estimate from operational weather forecasts of a 3.7°C cooling. The strongest surface climate effects were for ModelE configurations with more detailed aerosol microphysics that led to a stronger first indirect effect. Plain Language Summary: Smoke from biomass burning is known to have effects on surface weather. We used the NASA GISS ModelE to estimate these effects for a large 2017 smoke plume over northern Canada that persisted for two weeks. We first found that the height of the smoke release at the source was the most important factor influencing agreement between ModelE and satellite retrievals of aerosols and carbon monoxide, and that specific, plausible configurations of the model led to unrealistically high aerosol amounts. By comparing simulations with and without fire, we estimated a 16‐day cooling over a 850,000 km2 region of between 1.5°C and 4.9°C, depending on the model configuration. Key Points: We captured the overall pattern and magnitude of a large 2017 smoke plume over Canada with the NASA GISS ModelEOf the sixteen plausible model configurations tested under a full‐factorial design, two with higher NOx emissions, free‐tropospheric smoke release and mass‐based aerosols led to unrealistically high aerosol optical depthOver an 850,000 km2 region, we estimated a 16‐day surface cooling of between 1.5°C and 4.9°C [ABSTRACT FROM AUTHOR]

The use of acute carbon monoxide inhalation (COi) and hot water immersion (HWI) are of growing interest as interventions to stimulate erythropoietin (EPO) production. However, whether EPO production is further augmented when combining these stressors and whether there are sex differences in this response are poorly understood. Therefore, we measured circulating EPO concentration in response to acute COi and HWI independently and in combination and determined whether the responses were altered by sex. Participants completed three study visits—COi, HWI, and combined COi and HWI—separated by 1 week in a randomized, balanced, crossover design. Renal blood velocity was measured during all interventions, and carboxyhaemoglobin was measured during and after COi. Serum samples were analysed every hour for 6 h post‐intervention for EPO concentration. HWI decreased renal blood velocity (46.2 cm/s to 36.2 cm/s) (P < 0.0001), and COi increased carboxyhaemoglobin (1.5%–12.8%) (P < 0.0001) without changing renal blood velocity (46.4–45.2 cm/s) (P = 0.4456). All three interventions increased peak EPO concentration from baseline (COi: 6.02–9.74 mIU/mL; HWI: 6.80–11.10 mIU/mL; COi + HWI: 6.71–10.91 mIU/mL) (P = 0.0048) and to the same extent (P = 0.3505). On average, females increased EPO while males did not in response to COi (females: 6.17 mIU/mL; males: 1.27 mIU/mL) (P = 0.0010), HWI (females: 6.47 mIU/mL; males: 2.14 mIU/mL) (P = 0.0104), and COi and HWI (females: 6.65 mIU/mL; males: 1.76 mIU/mL) (P = 0.0256). These data emphasize that combining these interventions does not augment EPO secretion and that these interventions may work better in females. [ABSTRACT FROM AUTHOR]

The study examines the relationship between air quality, meteorological factors, and COVID-19 cases in Cheras, Kuala Lumpur, and Kelapa Gading, North Jakarta. Analyzing data from 2020 and 2021, the research found notable correlations: COVID-19 cases in Cheras were positively associated with relative humidity (RH) and carbon monoxide (CO) but negatively with ozone (O₃) and RH in different years. In Kelapa Gading, COVID-19 cases were positively correlated with pollutants like sulfur dioxide (SO₂) and CO, while ambient temperature (AT) showed a negative correlation. The enforcement of social restrictions notably reduced air pollution, affecting COVID-19 spread. Predictive models for PM2.5 levels using robust regression techniques showed strong performance in Kuala Lumpur (R² > 0.9) but exhibited overfitting tendencies in Jakarta, suggesting the need for a longer study period for more accurate results. [ABSTRACT FROM AUTHOR]

Over the past two decades, following the discovery of the important biological roles of carbon monoxide (CO), metal carbonyl complexes have been intensively studied as CO-releasing molecules (CORMs) for therapeutic applications. To improve the properties of "bare" low molecular weight CORMs, attention has been drawn to conjugating CORMs with macromolecular and inorganic scaffolds to produce CO-releasing materials (CORMAs) capable of storing and delivering large payloads of the gasotransmitter. A significant obstacle is to obtain CORMAs that retain the beneficial features of the parent CORMs. In the present work, a crystalline metal–organic framework (MOF) formulated as Mo(CO)3(4,4′-bipyridine)3/2 (Mobpy), with a structure based on Mo(CO)3 metallic nodes and bipyridine linkers, has been prepared in near quantitative yield by a straightforward reflux method, and found to exhibit CO-release properties that mimic those typically observed for molybdenum carbonyl CORMs. Mobpy was characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR, FT-Raman and diffuse reflectance (DR) UV-vis spectroscopies, and 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR. The release of CO from Mobpy was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. Mobpy liberates CO upon contact with a physiological buffer in the dark, leading to a maximum released amount of 1.3–1.5 mmol g−1, after 1.5 h at 37 °C, with half-lives of 0.5–1.0 h (time to transfer 0.5 equiv. of CO to Mb). In the solid-state and under open air, Mobpy undergoes complete decarbonylation over a period of 42 days, corresponding to a theoretical CO-release of 7.25 mmol g−1. [ABSTRACT FROM AUTHOR]

We have estimated the mass of metals in the molecular gas in 13 dusty star-forming galaxies at |$z \sim 4$| in which the gas, based on previous observations, lies in a cold rotating disc. We estimated the metal masses using either the submillimetre line or continuum emission from three tracers of the overall metal content – carbon atoms, carbon monoxide molecules, and dust grains – using the first simultaneous calibration of all three tracers. We obtain very similar mass estimates from the different tracers, which are similar to the entire metal content of a present-day massive early-type galaxy. We used the dynamical masses of these galaxies to estimate an upper limit on the mass of the molecular gas in each galaxy, allowing us to estimate a lower limit on the metal abundance of the gas, finding values for many of the galaxies well above the solar value. We show that the high metal masses and metal abundances are what is expected shortly after the formation of a galaxy for a top-heavy IMF. We suggest a scenario for galaxy evolution in which massive galaxies reach a high metal abundance during their formation phase, which is then gradually reduced by dry mergers with lower mass galaxies. We show that the metals in the outflows from high-redshift dusty star-forming galaxies can quantitatively explain the long-standing puzzle that such a large fraction of the metals in galaxy clusters (⁠|$\simeq$| 0.75) is in the intracluster gas rather than in the galaxies themselves. [ABSTRACT FROM AUTHOR]

Biomass burning plays an important role in climate-forcing and atmospheric chemistry. The drivers of fire activity over the past two centuries, however, are hotly debated and fueled by poor constraints on the magnitude and trends of preindustrial fire regimes. As a powerful tracer of biomass burning, reconstructions of paleoatmospheric carbon monoxide (CO) can provide valuable information on the evolution of fire activity across the preindustrial to industrial transition. Here too, however, significant disagreements between existing CO records currently allow for opposing fire histories. In this study, we reconstruct a continuous record of Antarctic ice coreCObetween 1821 and 1995CE to overlap with direct atmospheric observations. Our record indicates that the Southern Hemisphere CO burden ([CO]) increased by 50% from a preindustrial mixing ratio of ca. 35 ppb to ca. 53 ppb by 1995 CE with more variability than allowed for by state-of-the-art chemistry-climate models, suggesting that historic CO dynamics have been not fully accounted for. Using a 6-troposphere box model, a 40 to 50% decrease in Southern Hemisphere biomass-burning emissions, coincident with unprecedented rates of early 20th century anthropogenic land-use change, is identified as a strong candidate for this mismatch. [ABSTRACT FROM AUTHOR]

The application of electrochemical CO2 reduction reaction (CO2RR) to generate value‐added products, including carbon monoxide (CO), represents a sustainable strategy for addressing the global carbon balance. Silver (Ag) has gained significant attention as an attractive and cost‐effective electrocatalyst for CO2RR‐to‐CO due to high activity. Here, the porous Ag nanofoam catalysts with Ag(111)‐dominant were prepared by in‐situ electrolysis‐deposition method in the ionic liquid (IL) electrolyte. The Ag nanofoam catalysts exhibited exceptional activity in converting CO2 to CO, with a high Faradaic efficiency (>95 %) in a wide range of −1.9 ~ −2.4 V vs. Ag/Ag+ in the 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF4]) electrolyte. The maximum CO partial current density of −125.40 mA cm−2 was obtained on this Ag nanofoam catalyst, representing 62 % improvement over Ag(110)‐dominant Ag electrode (−77.35 mA cm−2) at −2.4 V vs. Ag/Ag+ in the [Bmim][BF4] electrolyte. Density functional theory calculations demonstrated that the Ag(111) crystal facet formed by in‐situ electrolysis‐deposition method prefers to adsorb [Bmim][BF4] which can stabilize the reaction intermediate, thereby weakening the reaction free energy and promoting CO2 electroreduction. [ABSTRACT FROM AUTHOR]

The problem of nitrogen oxide (NOx) emissions has attracted wide attention in the field of environmental protection. The effects of sodium hydroxide (NaOH), hydrogen peroxide (H2O2), phenol (C6H5OH) and ethanol (C2H6OH) on the denitration activity of selective non‐catalytic reduction (SNCR) and the emission of secondary pollutants nitrous oxide (N2O) and carbon monoxide (CO) were investigated. Results indicated that the addition of NaOH, phenol and ethanol can improve the denitration efficiency under low temperature by providing OH. From 650°C to 750°C, ethanol had the best effect, with the denitration efficiency of 30%. From 750°C to 850°C, the denitration efficiency of phenol was 40% ~ 50%. The introduction of phenol and ethanol would increase the N2O and CO emissions. From 700°C to 800°C, hydrogen peroxide only caused a small amount of N2O emissions and had no significant effect on CO. [ABSTRACT FROM AUTHOR]

Palladium‐catalyzed thioesterification of (aza)indole‐tethered aryl iodides, Mo(CO)6, and sulfonyl chlorides is reported. A series of C2 thioester‐group substituted indoline‐fused ring compounds are constructed by an intramolecular Heck cyclization and carbonylation chemistry involving N‐(2‐iodobenzoyl)indole. The salient features of this three‐component cascade sequence include the use of solid Mo(CO)6 as the carbon monoxide source and good functional group tolerance. [ABSTRACT FROM AUTHOR]

To test the hypothesis that an abiotic Earth and its inert atmosphere could form chemically reactive carbon-and nitrogen-containing compounds, we designed a plasma electrochemical setup to mimic lightning-induced electrochemistry under steady-state conditions of the early Earth. Air-gap electrochemical reactions at air-water-ground interfaces lead to remarkable yields, with up to 40 moles of carbon dioxide being reduced into carbon monoxide and formic acid, and 3 moles of gaseous nitrogen being fixed into nitrate, nitrite, and ammonium ions, per mole of transmitted electrons. Interfaces enable reactants (e.g., minerals) that may have been on land, in lakes, and in oceans to participate in radical and redox reactions, leading to higher yields compared to gas-phase-only reactions. Cloud-to-ground lightning strikes could have generated high concentrations of reactive molecules locally, establishing diverse feedstocks for early life to emerge and survive globally. [ABSTRACT FROM AUTHOR]

Diesel generators are widely used to produce electricity and heat in remote communities. However, their use contributes to harmful pollutant and greenhouse gas (GHG) emissions, negatively impacting the environment and public health. Syngas, which is a sustainable fuel, can play an important role in the transition from petroleum to renewable fuels. When used in dual-fuel diesel engines, it can contribute to reducing GHG emissions and the cost of transporting diesel, especially for rural and remote communities. This study investigates the effects of optimizing the diesel direct injection (DI) and exhaust gas recirculation (EGR) strategies on the combustion and emission performance of a syngas-diesel dual-fuel generator at constant load. The experiments were conducted using a 30-kW generator with a four-stroke, four-cylinder, turbocharged, and electronically controlled direct-injection diesel engine. The intake manifold of the engine was modified to allow introducing syngas upstream of the turbocharger. The syngas was simulated using individually controlled flow rates of hydrogen (H 2), carbon monoxide (CO), carbon dioxide (CO 2), and nitrogen (N 2). The syngas flow rate was adjusted to replace 40% of the energy provided by diesel fuel while optimizing the diesel DI parameters such as the pilot injection timing, main injection timing and diesel direct injection rail pressure, as well as the EGR rate. The findings of this study reveal that optimizing diesel injection strategy and appropriately raising the EGR rate have a positive impact on the engine performance and emissions. • Optimizing diesel injection strategies and EGR rate of a syngas-diesel dual-fuel diesel engine. • Hydrogen-rich syngas enhances combustion efficiency and emissions control. • Fine-tuning of pilot injection timing and duration improved the engine efficiency and emissions. • Increasing EGR rate stabilized emissions, with notable reductions in NOx and CO levels. • Adjustment of the main injection timing positively impacted combustion characteristics. • Increasing the injection pressure resulted in notable reductions in CO and PM emissions. [ABSTRACT FROM AUTHOR]

Background and Aims: Sleep‐disordered breathing (SDB) and nocturnal hypoxemia were known to be present in patients with chronic thromboembolic pulmonary hypertension (CTEPH), but the difference between SDB and nocturnal hypoxemia in patients who have chronic thromboembolic pulmonary disease (CTEPD) with or without pulmonary hypertension (PH) at rest remains unknown. Methods: Patients who had CTEPH (n = 80) or CTEPD without PH (n = 40) and who had undergone sleep studies from July 2020 to October 2022 at Shanghai Pulmonary Hospital were enrolled. Nocturnal mean SpO2 (Mean SpO2) <90% was defined as nocturnal hypoxemia, and the percentage of time with a saturation below 90% (T90%) exceeding 10% was used to evaluate the severity of nocturnal hypoxemia. Logistic and linear regression analyses were performed to investigate the difference and potential predictor of SDB or nocturnal hypoxemia between CTEPH and CTEPD without PH. Results: SDB was similarly prevalent in CTEPH and CTEPD without PH (P = 0.104), both characterised by obstructive sleep apnoea (OSA). Twenty‐two patients with CTEPH were diagnosed with nocturnal hypoxemia, whereas only three were diagnosed with CTEPD without PH (P = 0.021). T90% was positively associated with mean pulmonary arterial pressure (mPAP) and pulmonary vascular resistance in patients with CTEPH and CTEPD without PH (P < 0.001); T90% was also negatively related to cardiac output in these patients. Single‐breath carbon monoxide diffusing capacity, sex and mPAP were all correlated with nocturnal hypoxemia in CTEPH and CTEPD without PH (all P < 0.05). Conclusion: Nocturnal hypoxemia was worse in CTEPD with PH; T90%, but not SDB, was independently correlated with the hemodynamics in CTEPD with or without PH. [ABSTRACT FROM AUTHOR]

An emerging area of study known as Cognitive IoT (CIoT) has emerged as a result of recent efforts to include cognition in the design of the Internet of Things (IoT). Several features and challenges from the IoT are carried over to the CIoT. A lot of applications in CIoT generate massive heterogeneous data, and they require inferential tasks with less computational overhead. Therefore, this study suggests a decentralized computing approach to handle multiple hypothesis testing in less computational time. The first stage is to minimize error at the cluster node by total variance regularization through the alternating direction method of multipliers. Subsequently, the fusion center handles the heterogeneity of data, minimizes model error, extracts the most informative data, and adjusts the p-value for multiple hypotheses testing. The experimental evaluation and cross-validation on six-month traces of the carbon monoxide dataset reveal the efficacy of the proposed algorithm over competing approaches. [ABSTRACT FROM AUTHOR]

Despite the extensive research on biodiesels, further investigation is warranted on the impact of compression ratios on emissions and engine performance. This study addresses this gap by evaluating the effects of increasing the engine's compression ratio on engine performance metrics—brake-specific fuel consumption (BSFC), power, torque, and exhaust gas temperature—and emissions—unburnt hydrocarbons (HCs), carbon dioxide (CO2), carbon monoxide (CO), nitrogen oxides (NOx), and oxygen (O2)—when fueled with a 20% blend of waste cooking oil biodiesel (WCB20) and petroleum diesel (PD) under various operating conditions. The viscosity of the prepared fuels was measured at 25 °C and 40 °C. Experiments were conducted on a single-cylinder diesel engine under wide-open throttle conditions at three different speeds (1400 rpm, 2000 rpm, and 2600 rpm) and two compression ratios (16:1 and 18:1). The results revealed that at a lower compression ratio, both WCB20 and petroleum diesel exhibited reduced BSFC compared to higher compression ratios. However, increasing the compression ratio from 16:1 to 18:1 significantly decreased HC emissions but increased CO2 and NOx emissions. Engine power increased with engine speed for both fuels and compression ratios, with WCB20 initially producing less power than diesel but surpassing it at higher compression ratios. WCB20 demonstrated improved combustion quality with lower unburnt hydrocarbons and carbon monoxide emissions due to its higher oxygen content, promoting complete combustion. This study provides critical insights into optimizing engine performance and emission characteristics by manipulating compression ratios and utilizing biodiesel blends, paving the way for more efficient and environmentally friendly diesel engine operations. [ABSTRACT FROM AUTHOR]

This study aims to provide an overview of the growing need for renewable energy conversion and aligns with the broader context of environmentally friendly energy, specifically through producing syngas from biomass. Unlike natural gas, which is mainly composed of methane, syngas contains a mixture of combustible CO, H2, and CnHm. Therefore, optimizing its production requires a thorough examination of various operational parameters such as the gasifying agent, the equivalence ratio, the biofuel type, and the state, particularly in densified forms like pellets or briquettes. As new biomass sources are continually discovered and tested, operational parameters are also constantly evaluated, and new techniques are continuously developed. Indeed, these techniques include different gasifier types and the use or non-use of catalysts during biofuel conversion. The present study focuses on these critical aspects to examine their effect on the efficiency of syngas production. It is worth mentioning that syngas is the primary gaseous product from gasification. Moreover, it is essential to note that the pyrolysis process (prior to gasification) can produce, in addition to tar and char, a mixture of gases. The common feature among these gases is their versatility in energy generation, heat production, and chemical synthesis. The analysis encompasses the resulting gas features, including the yield and composition, mainly through the hydrogen-to-carbon monoxide ratio and the carbon monoxide-to-carbon dioxide ratio, as well as the lower heating value and considerations of the tar yield. [ABSTRACT FROM AUTHOR]

In order to study the cruise safety of aircraft under high altitude and low pressure, the combustion characteristics of protective cover and insulation layer of waxy aviation cable FXL under normal pressure and low pressure are studied in this paper. The minimum ignition time (TTI), the maximum radiation temperature, the flue gas density and the mass loss rate of the protective cover and insulation layer of the waxy FXL aviation cable under 96 kPa and 61 kPa were studied. It is found that the minimum radiation temperature and TTI of the cable at 61 kPa are slightly higher than those at 96 kPa, but the activation energy is basically not affected by the air pressure. The smoke density and smoke composition under 96 kPa and 61 kPa were further studied, and it was found that the smoke density of the cable under 61 kPa sheath and insulation layer was lower than that under 96 kPa. The oxygen, carbon dioxide and carbon monoxide components in the flue gas were studied. It was found that the O2 concentration of 96 kPa and 61 kPa cable protective sleeve and insulation layer decreased steadily at first and then increased. The change trend of CO2 concentration was opposite, and the CO concentration showed a double-peak phenomenon. In addition, the mass loss rate (MLR) at different O2 concentrations increases linearly with the increase in O2 concentration. This work helps to understand the difference of combustion characteristics between 96 and 61 kPa, and provides a reference for improving civil aviation safety performance. [ABSTRACT FROM AUTHOR]

High-energy–density fuel exo-tetrahydrodicyclopentadiene (exo-THDCPD) has high density and calorific value, which has the potential to be used as an extended-range fuel to improve the maneuverability and endurance of ground vehicle equipment. The present experiment aimed to investigate the combustion, performance and emission characteristics of different exo-THDCPD/diesel blends to explore the feasibility of its application in diesel engine. The test fuels were prepared on volume basis and named as follows: ED5, ED10, ED15, ED20 and ED25. The tests were carried out on a six-cylinder, four-stroke, naturally aspirated and direct injection diesel engine. It was observed that the blends had higher brake thermal efficiency, torque compared to pure diesel, while lower brake specific fuel consumption. Combustion analysis indicated that exo-THDCPD/diesel blends had longer ignition delay, shorter combustion duration, higher in-cylinder pressure and heat release rate, suggesting improved combustion. Furthermore, the coefficient of variation in maximum in-cylinder pressure and the coefficient of variation in indicated mean effective pressure increased as exo-THDCPD ratios increased, but all the values were no more than 5%, indicating a relatively stable combustion. In terms of exhaust emissions, nitrogen oxide, unburned hydrocarbon and carbon monoxide emissions increased significantly with exo-THDCPD/diesel blends compared to pure diesel, while soot emissions decreased. [ABSTRACT FROM AUTHOR]

Objectives SLE is a systemic autoimmune disease characterized by heterogeneous manifestations and severity, with frequent lung involvement. Among pulmonary function tests, the measure of the diffusing capacity of the lungs for carbon monoxide (DLCO) is a noninvasive and sensitive tool assessing pulmonary microcirculation. Asymptomatic and isolated DLCO alteration has frequently been reported in SLE, but its clinical relevance has not been established. Methods This retrospective study focused on 232 SLE patients fulfilling the 2019 EULAR/ACR classification criteria for SLE. Data were collected from the patient's medical record, including demographic, clinical and immunological characteristics, while DLCO was measured when performing pulmonary function tests as part of routine patient follow-up. Results At the end of follow-up, DLCO alteration (<70% of predicted value) was measured at least once in 154 patients (66.4%), and was associated with a history of smoking as well as interstitial lung disease, but was also associated with renal and neurological involvement. History of smoking, detection of anti-nucleosome autoantibodies and clinical lymphadenopathy at diagnosis were independent predictors of DLCO alteration, while early cutaneous involvement with photosensitivity was a protective factor. DLCO alteration, at baseline or any time during follow-up, was predictive of admission in intensive care unit and/or of all-cause death, both mainly due to severe disease flares and premature cardiovascular complications. Conclusion This study suggests a link between DLCO alteration and disease damage, potentially related to SLE vasculopathy, and a prognostic value of DLCO on death or intensive care unit admission in SLE. [ABSTRACT FROM AUTHOR]

Photoactivatable carbon monoxide‐releasing molecules (CORMs), typically based on transition‐metal carbonyl complexes, have reliance on activation by UV or visible light that restricts their biomedical applications. To address this limitation, a near‐infrared (NIR)‐responsive nanoplatform is presented based on upconversion nanoparticles (UCNPs) loading with manganese carbonyl complex Mn2(CO)10 that concurrently releases CO and manganese ion (Mn2+). With the UCNPs, the more tissue‐penetrable NIR is used to locally generate UV light for photodecomposition of Mn2(CO)10 into CO and manganese oxide (MnOX), after which MnOX is reduced to Mn2+ by the overexpressed glutathione in cancer cells. Moreover, the released Mn2+ can serve as a magnetic resonance imaging contrast agent to monitor the NIR‐controlled corelease of CO and Mn2+ in real time. Therefore, this nanoplatform can provide a potential strategy for NIR‐enabled spatiotemporally release of CO and Mn2+, enhancing the controlled delivery and biomedical application of CORMs. [ABSTRACT FROM AUTHOR]

The discovery of new classes of regulatory molecules in human and animal metabolism always leads to a large-scale study of their properties in the context of biochemistry, physiology, and pharmacology. About 20 years ago, hydrogen sulfide (H2S) and its derivatives called reactive sulfur species (RSS), such as persulfides, polysulfides, nitrosothiols, sulfenic acids, and others became one of such classes of molecules. The participation of RSS in a variety of physiological and pathological processes, including the regulation of vascular tone, inflammation, long-term potentiation in the central nervous system, etc., has been shown. Changes in RSS levels or patterns of modification of their targets are associated with a wide range of cardiovascular, oncological, neurodegenerative, and other pathologies. For a part of these processes, mechanisms have been studied that involve direct modification of regulatory (NF-κB, Keap1) or effector (GAFD, eNOS, TRPA1) proteins through reactions of cysteine residues and metal-containing centers with APS. The presence of different regulated enzymatic systems producing RSS and numerous molecular targets allows us to consider H2S and its derivatives as an important class of small regulatory molecules. H2S is belongs to the class of so-called "gasotransmitters," along with nitric oxide (II) and carbon monoxide. Over the last 20 years, a vast amount of data on the biochemistry of these compounds and approaches to their study has been accumulated. [ABSTRACT FROM AUTHOR]

Current guidelines for prolonged altitude exposure suggest altitude levels ranging from 2000 to 2500 m to optimize an increase in total hemoglobin mass (Hbmass). However, natural low altitude locations (<2000 m) remain popular, highlighting the interest to investigate any possible benefit of low altitude camps for endurance athletes. Ten elite racewalkers (4 women and 6 men) underwent a 4‐week "live high‐train high" (LHTH) camp at an altitude of 1720 m (PIO2 = 121 mmHg; 20.1°C; 67% relative humidity [RH]), followed by a 3‐week tapering phase (20 m; PIO2 = 150 mmHg; 28.3°C; 53% RH) in preparation for the World Athletics Championships (WC). Venous blood samples were withdrawn weekly during the entire observation period. In addition, blood volumes were determined weekly by carbon monoxide rebreathing during altitude exposure and 2 weeks after return to sea level. High‐level performances were achieved at the WC (five placings among the Top 10 WC races and three all‐time career personal bests). A slight but significant increase in absolute (+1.7%, p = 0.03) and relative Hbmass (+2.3%, p = 0.02) was observed after 4‐week LHTH. In addition, as usually observed during LHTH protocols, weekly training distance (+28%, p = 0.02) and duration (+30%, p = 0.04) significantly increased during altitude compared to the pre‐LHTH period. Therefore, although direct causation cannot be inferred, these results suggest that the combination of increased training load at low altitudes with a subsequent tapering period in a warm environment is a suitable competition‐preparation strategy for elite endurance athletes. Highlights: Despite current guidelines for prolonged altitude exposure, natural low altitude locations (<2000 m) remain popular among elite endurance athletes, highlighting the interest to investigate any possible benefit of low altitude camps.This study reports that elite racewalkers achieved a modest but significant increase in Hbmass after a 4‐week LHTH camp at an altitude of 1720 m. Furthermore, this intervention led to performance success at the subsequent World Athletics Championships.The combination of an increased training load while exposed to low altitude is suggested as a valuable competition preparation strategy for elite endurance athletes. [ABSTRACT FROM AUTHOR]

The Asian summer monsoon anticyclone (ASMA) plays a vital role in the transport and redistribution of the tracers in the upper troposphere and lower stratosphere during transient monsoon conditions. The ASMA can be identified using various diagnostics such as winds and divergence, potential vorticity, the Montgomery stream function or geopotential height. Its representation based on the commonly‐used existing method that takes a climatological range of the geopotential height (GPH) at a given pressure level is not robust and fails in several circumstances. In this study, we propose a new GPH method to define the ASMA for the active and break phases of the monsoon based on the GPH values at the tropical easterly jet (TEJ) and subtropical westerly jet (STJ) locations. The proposed method compares the GPH values at the locations corresponding to the wind speed maxima of TEJ and STJ at 100 hPa with the maximum GPH at 100 hPa and selects the one with the minimum difference to define the ASMA extent. The same procedures were applied to obtain the ASMA extent at 150 hPa. The ASMA extents are obtained using the method proposed here and the existing fixed GPH method for the 30 active and 27 break phases from 2005 to 2023. The fixed GPH method provides a larger ASMA extent for 24 active and 21 break phases, which appears to be an unrealistic estimation compared to the proposed method. Our proposed method identifies the ASMA extent that is larger and centred around the Iranian side during the active phases while it is smaller and centred around the Tibetan side during the break phases. Furthermore, the minimum concentration of ozone (O3), and maximum concentrations of carbon monoxide (CO) and water vapour (H2O) are also found to be centred near the Iranian side during the active phases and on the Tibetan side during the break phases. The tracer concentrations are generally higher for CO, H2O and O3 during the active phase than in the break phase. Tracer concentrations within the ASMA extent using the fixed GPH method are higher for O3 while lesser for CO and H2O when compared to the proposed method. [ABSTRACT FROM AUTHOR]

Clostridium autoethanogenum is a model microbe capable of converting carbon monoxide (CO) into bioethanol and useful biochemicals. Successful process optimization when using CO as the primary carbon source requires an understanding of the influence of process parameters and growth medium components on cell growth and end‐product formation. We conducted a full factorial analysis of the effects of CO total pressure, pH, yeast extract (YE), and cysteine concentrations on acetic acid, ethanol, and biomass production utilizing C. autoethanogenum with CO as the primary substrate. Maximum ethanol production of 0.71 g L–1 was obtained at a pH of 4.5, yeast extract concentration of 0.5 g L–1 , CO pressure of 1.8 atm, and cysteine concentration of 1.5 g L–1. There was a tenfold enhancement when the pH was lowered from 6 to 4.5 and the YE concentration was reduced to 0.5 g L–1. Response optimization using the reduced gradient algorithm confirmed these results. The information presented in this study could prove valuable for process engineering design by assisting with the selection of parameters that yield syngas blends specifically intended for increased ethanol production. [ABSTRACT FROM AUTHOR]

The global incidence and prevalence of arrhythmias are continuously increasing. However, the precise mechanisms of underlying arrhythmogenesis and the optimal measures for effective treatment remain incompletely understood. The inducible form of heme oxygenase, known as heme oxygenase-1 (HO-1), is recognized as a potent antioxidant molecule capable of exerting anti-inflammatory and anti-apoptotic effects. Recent research indicates that HO-1 plays a role in preventing arrhythmias by mitigating cardiac remodeling, including electrical remodeling, ion remodeling, and structural remodeling. This review aimed to consolidate current knowledge regarding the involvement of HO-1 in arrhythmias and elucidate its underlying mechanisms of action. [ABSTRACT FROM AUTHOR]

The radiolysis of liquid and boiling hexafluoroacetylacetone has been studied. The structure of the main radiolysis products indicates the predominance of C–CF3 and C–F bond cleavages. Ten compounds including monoketones, trifluoroacetic acid, keto alcohols, and tautomeric tetraketones were formed. Carbon monoxide was the main gaseous product, and its yield increased under boiling conditions. The initial yields of hexafluoroacetylacetone degradation were 0.29 ± 0.2 and 0.32 ± 0.2 µmol/J at 293 and 343 K, respectively. No accumulation of free HF was observed at low doses. The products of radiolysis are less diverse than those in acetylacetone; this is due to enhancement of the cage effect and to an increase the Onsager radius and the ability of trifluoromethyl groups to dissipate excitation energy. [ABSTRACT FROM AUTHOR]